Synthetic resins photographic process, media, and process of preparing same



Patented June 1, 1926.

UNITED STATES PATENT oFFrcE.

MURRAY 0. BEE-BE, ALEXANDER MURRAY, AND HAROLD V. HERLINGER, OF CINCIIIN- NATI, OHIO, ASSIGNORS TO THE 'WADSWOR'IH WATCH CASE COMPANY, OF DAYTON, KENTUCKY, A CORPORATION" OF KENTUCKY.

SYNTHETIC nnsms rnoroennrmo raoonss, MEDIA, AND rnocnss or PREPARING 4 samz.

1T0 Drawing.

. The invention constitutes a. species of the 5 generic invention pertalnlng to the use, for

photographic purposes, of condensation products derived from the monoheteratomic five-membered ring compounds, set forth in our pending application No. 601,827, filed November 18, 1922; and the application just referred to constitutes, in turn, a species of the generic invention set forth and claimed in our application No. 613,795, filed January .17, 1923.

The purpose of the present invention is to provide for the use, for photographic purposes, or. a medium, which,- comparatively speaking, is very rapid in the trans formation which occurs under the action of light transmitted to, or projected-upon, the medium in accordance with 'a luminous image.

In the presentinvention, we make use principally of condensation products, or resins, derived from a five-membered monoheterocyclic compound, preferably furfural, and anamine body; and the amine body which it is preferred to employin obtaining the resin which is to be embodied in the combined with furfural, for example, to produce resinous substances. The reagents there men-cloned include some of the amines,

' such as ammonia, .alpha-napthylamine, and.

aniline. The present invention utilizes ingredients which, in some instances, appear tobe' addition'products, as distinguished from actual preliminary. condensation products.- Nevertheless, these addition products, if such they "photographic medium preferably is B'-naph-- very desirable sensitizer.

made to numerous reagent's'which may bev Application filed January 19, 1923. Serial No. 618,796.

be, are found to be in suitable physical form to. enable them to be used in a photographic medium, and are in suitable. condition to enable them to be readily transformed under the selective action of light in accordance with a luminous image, design or character. 1 While the use of the product derived from -naphthylamine and furfural is preferred, numerous other examples are set forth herein of resins derived from furfural and amine bodies which may be regarded as practical equivalents for thepurposes of the present invention.

For the purpose of enabling the invention to be understood and ascertained. the following description is given, setting forth various exemplifications:

While, in general, resins derived from furfural are quite light-sensitive, nevertheless, it may be useful to employ sensitizers in conjunction with-these resins, or some of them. It has been found to be .the case, particularly in the resins derived from furfural and the amine bodies, that the use of sensitizers is desirable. Various sensitizers maybe employed, Rreferably the sensitizer will comprise a halogen source, or a halogenliberating compound. A halogen-substituted hydrocarbon. such as iodoform, affords a Such sensitizers serve to accelerate the transformation which occurs under the selective action of light transmitted, or projected, upon the scumtive body in accordance with a luminous image, design or character. Halogen is liberated under the action of light and,

I doubtless, acts as a catalyzer, hastening the reaction. a

We have found that in this B-naphthylamine furfural process a mixture of the two ingredients indicate no condensation at room "temperature, and yet the mixture is in suitable physical condition to use as a coating in whichthe actual I condensation willpractically not take place until lodine is liberated from a sensitizer, such as iodoform. When the iodine constituent is liberated by light, the coating condenses rapidly forming an exceedingly rapid printing medium. If B-naphthylamine and furfural are mixed together, they form a solid substance inside of a few minutes that has- "soluble in benzol. grams of the mixture dissolved in 100 cc. of benzol forms a solution, from which 20 grams addedto one gram of iodoform produced a light-sensitive coat ingwhich gave prints in from one-fifth to one-tenth of the time required for a furfural acetone coating, and the prints are developed with great facility in turpentine or alcohol and water. In contrast to the furfural acetone process, iodoform in this case is a rapid sensitizer. This sensitization is so marked that we have found it exceedingly diflicult to get any kind of print without the use of the iodoform.

Without limiting ourselves to a disclosure of the ultimately exact chemical reactions, it appears that the first action in combining B-naphthylamine and furfural is a solvation step, even though the product is solid and has a resinous appearance, because the B- naphthylamine can still be dissolved out of the mixture by water which is not the case after condensation has actually occurred. In other words, it is believed that furfural and B-naphthylamine form an unstable addition product when mixed and really only condense under the influence of iodine and the action of light. It may also be said that the B-naphthylamine crystals when mixed into the furfural immediately go into solution fairly completely at room temperature, and that no actual condensation takes place until the tem erature is increased to near 100 degrees or unless free iodine or a halogen catalyzer be added. The iodoform under the action of light liberates iodine which immediately starts real condensation withgreat rapidity. This speed is probably dependent practically upon the rate at which the iodine is liberated from the iodoform, indicating that additional speed in rinting action ma be dependent more or ess on the catalyzin liberation of iodine from'iodoform-by lig 1;.

E uimolecular proportions of ,furfural and -naphthylam1ne work as well as the proportions noted above. We have also found that there are other combinations which give practical results as follows:

15 parts of B-naphthylamine and ,10 parts of furfural are mixed to form a solid mass at room' temperature.. Enou' h of .this is dissolved'inlnaphtha; tomake a ut a 23 percent solution. To 50 grams of the above solution, 5 grams of iodoform and A cc. of

eugenol is added. This forms a coating that then diluted with 500 cc. of solvent naphtha,

and filtered. A portion remains insoluble in the solvent naphtha but it can be dissolved in ethyl methyl ketone, and it is quite insensitive to light. To 50 grams of the solvent naphtha solution, 2 grams of iodoform and 1 gram of eugenol-are added to form a coating which contains approximately 10 per cent of the resin.

We have also determined the relative value of ammonium bichromate as a sensitizer and have found that it accelerates the condensation under the action of light very slightly, being less reactive than iodine, indicating a sensitivity that is but very little more than that of the resin itself, which requires about ten minutes to obtain a very poor print.

When furfural and aniline are mixed at room temperature, they react to form a yellow precipitate combined with some water.

given 011' by the reaction. By dehydratingthis precipitate with a substance such as calciumchloride, the water is eliminated and a sticky mass remains which is an addition product analogous to that obtained by the interaction of furfural and B-naphthylamine. Such an addition product dissolves in benzol, and, when sensitized by means of iodoform, produces a light sensitive coating on which prints are produced in lessthafii a minute. I A

Benzaldehyde has come to be considered somewhat analogous to furfural in most of its reactions, although it belongs to a different groupof organic compounds. 10 grams of this substance and 20 grams of B naphthylamine when mixed-*at room temperature also form an addition product that is solid and resembles that formed by furfuralandB-naphthylamine. -Such a prodthe previous exemplifications. We formed a coating mixture by taking 20 grams of B-naphthylamine'and 30 grams of formalin .precipitate addition product which resembles solution and made a 20 percent solution in acetone. 20 cc. of this mixture was sensitized with 2 grams of-iodoform, producing good prints in fifteen seconds.

The various exemplifications of printing conditions.

time, etc., all relate to similar illuminating y The printing of an image, whether by contact or'by optical projection, is so well understood in the art that the same is not described.

We have also found that a mixture of two substances, forming an additional product, when free iodine is added, under the action oflight, condenses to a resin proportional to the varying intensity of the light. This is exemplified as follows: An addition product of furfural-B-naphthylamine is a pink ish appearing solid substance. If this is heated, it condenses to a dark brown resin which was not expected to print as rapidly as the addition product. By itself it is not sensitive, but by the addition of a little iodob form it is fully as sensitive as the other compounds. This step has been exemplified in theeugenol adaptation above. From this it is believed that the reaction in all of these exemplifications is simply the formation of a condensation products of the synthetic resin by the halogen under the action of light. Some compounds print faster than others" and an explanation of this variableness to.

light action has not as yet. been found, but many of those described and probably numerous other related compounds are rapid enoughto form commercially available processes.

' Our light-sensitivemixtures may be applied to the desired surfaces as a coating in any well known manner by flowing, brushing, whirling, etc. Since these steps in and of themselves do not constitute a part of this invention, they are not described in detail, and we do not confine or limit ourselves to any of these or other expedients.

In addition to the previous B-naphthylamine-furfural exemplications, we have also found that the following adaptations of other ingredients produce light-sensitive mixtures which have been used to produce prints under similar lighting'con-ditions as in the previous exemplifications in the times indicated under each exemplification.

lVhen 19.6 grams of cyclohexanone and 38.4 grams of furfural are combined with h grams of furfural are mixed at room temperature' and are allowed to stand 1 about e in the solvent to make a uces a mixture that, when.

twelve hours to form a hard and brittle resin. A 20% solution of the resin in benzol, after standing about one-half hour, forms a light-sensitive mixture, which, through the addition of one gram of iodoform to 20 cc. of such solution, is printable in from 10 to 30 seconds, and is developed in a 5050 benzol-benzine solvent. The resin, without the addition of a sensitizer, under the same exposure, etc.,'produces a similar print in about four minutes; 1

A para-toluidine-furfural adaptation is carried out by heating 20 grams of paratoluidine and 10 grams of furfural on a hot plate'for 21/ hours to a temperature of about 150 degrees C. This produces a hard dark rown resin. A 20% solution of this is made in acetone, and 2Ucc. of this solution, when sensitized with 1 gram of iodoform, prints in about three minutes, and is. also developed in 5050'-benzol-benzine.

We have also combined 20 grams of ben-' zidine and 20 grams of furfural at room temperature to form a resinous mass. A 20% solution was made in ethyl methyl ketone and 20 cc. of this solution was sensitized with 1 gram of iodoform, producing a mixture that gave prints in from three to ten seconds that were also developed as in the preceding exemplification.

A hard brittle resinis'formed in 2% to 3' hours at room' temperature through the re- 4 action of 25 grams each of metaphenylenediamine (technical) and furfural- 20 cc. of a 20% solution of the resin in acetone, sensitized by 1 gram of iodoform, prints in from 5 to 20 seconds. These prints are developed in 80 parts of benzol and 20 parts of benzine.

We have also combined xylidine (tec-hnivca-l) and furfural.

The reaction of 25 grams of each is similar to that of aniline and furfural. 10cc. of the mixture in 2 cc. ofbenzol and gram of iodoform produces a light-sensitive mixture that prints by pro jection in 30 to 60 seconds. When a single drop of a 9% solution of idodine in benzol is added to xylidine furfural mixture, there results a thick viscous mass in about 48 ours. 20 grams of this, when sensitized with 1 grain of iodoform and thinned with 15 cc. o f benzol, will form a coating that prints in 30 seconds and which maybe developed in turpentine.

We have produced a lightsensitive niixture that without the use of a sensitiger produces prints similar to our furfural-acetone coatings, heretofore referred ,to, in i from 30 seconds to 3 minutes, depending upon the character-of the negative and the metal upon which it' is printed, the lightlng conditions being similar to other exemplifications referred to above. Th s alternative or equivalent resin was formed by mixing 10 grams of mesltyloxideand 30 grams of furfural with 5 grams of a 10% solution of caustic soda in a reflux condenser under gentle heat. After neutralization with hydrochloric acid, the resulting resin was baked at 115 degrees C. for hours, after which grams of the resin were dissolved 'exemplifications, we have found that cyclohexane-carboxylic and furfural "act similarly to cyclohexanone and furfural. In any of these exemplifications, we do not limit ourselves to the use of special developing agents where such are specifically mentioned. In other cases, where no developing agent is referred to, any suitable cooperating developer may be employed, such as halogen-liberating agents, etc. a

In our use of furfural acetone and mesityl-oxide furfural coatings, we have found present in developed prints a very delicate crackling effect formed in the coating in a selective manner, being quite analogous 'to' the early forms of aquatint ground and more remotely similar togelatinous, reticulation. These delicate irregularly formed cracks expose the bare metal to the action of whatever mordant may be used, and they appear to lend themselves specially to the production of photo or rotogravures;

- It is not improbable that the effect of the light on our sensitive coating is such that the sensitizer sets free variable quantities of catalyst-so as to cause selective condensation' of the addition compounds and thereby reproduce the image which has been projected on the coating in an optical manner through space or in contact therewith.

While it is preferred to employ solutions of the resins, so that such solutions can be readily applied as a coating to any suitable surfaces, the invention is not to be understood as limited in this respect. As will readily occur to those skilled in the art of photographic processes as employed for in dustrial purposes, the present invention may be put to many difierent useful applications. I I

It will be understood, of course, that the film, or image, may .be developed, or fixed,

prises: acting selectively with light in accordance with an image, design or character in any suitable manner.

*In our pending application No.[601,827,

' filedNovember 18, 1922, reference is made to. the use of A-naphthylamine in, connection with furfural to produce a resin suitable for photographic purposes. The B-naphthvlamine furf ural-resin .is, however, more rapid in its action, and is preferred. In our application No. 613,795, filed January 19, 1923, reference is made to the use of other amine bodies. for example, di-

methyl-aniline and benzyl-aniline. Suchbodies may be employed within the scope of the present invention.

Also, in our application No. 601,827, it is pointed out that furfural is included with pyrrol and thiophene in a class, or, group of substances, constituting five-membered m'ono-heterocyclic compounds. These substances are to be regarded as equivalents, in the broad sense. The foregoing detailed description has been given for clearness of understanding only, and no unnecessary limitations should be understood therefrom, but the appended claims should be construed as broadly as permissible.

What we regard as new, and desire to secure by Letters Patent, is

1. A photographic process which 'comprisesz-acting selectively with light in accordance with an image, design or' character upon a resinous compound derived from an amine and a five-membered mono-heterocyclic compound. I

2. A photographic process which comprises: acting selectively with light in accordance with an image, design or character upon a resinous compound derived from an amine and a five-membered mono-heterocyclic compound, and developing the print.

3. A photographic process which. comprises: acting selectively with light in accordance with an image, design or character upon a resinous compound derived from an amine and furfural. v

4. A photographic process which comprises: acting selectively with light in accordance with an image, design or character upon a resinous compound derived from an amine and furfural, and developing the print. y

5. A photographic process which comprises: acting selectively with light in accordance with an image, design or character upon a resinous compound derived from naphthylamine and a five-membered monoheterocyclic compound.

6. A photographic process which comprises: actingselectively with light in accordance with an image, design or character upon a resinous compound derived frornB- naphthylamine and a five-membered monoheterocyclic compound.

17. A photographic process which comupon a resinous compound derived from B- naphthylamineand a five-membered monohetero'cyclic compound, and developing the 10. A photographic process which com prises: acting selectively with light in accordance with an image, design or character upon a compound which comprises a resinous material derived from an amine and a fivemembered mono-heterocyclic compound, associated with a sensitizing agent.

11. A photographic process which comprises: acting selectively with light in ac cordance with an image, design or character upon a compound which comprises a resinous material derived from an amine and a fivemembered mono-heterocyclic compound, associated with a sensitizing agent comprising a halo ensource.

12. photographic process which comprises: acting selectively with light in ac cordance with an image, design or character upon a compound which comprises a resinous materialderived from an amine and a five membered mono-heterocyclic compound, as-

sociated with a sensitizing agent comprising a halogen-liberating compound.

13. A photographic process which com prises: acting selectively with light in ac-.

cordance with an image, design or character upon a compound which comprises a resinous material derived from an amine and a fivemembered mono-heterocyclic compound, as-

sociated with a sensitizing agent comprising .,pound derlved from an amine and a fivemembered mono-heterocyclic compound, said body having incorporated therewith a sensitizing agent, and developing the print.

16.. A photographic process which comprises: acting selectively with light in accordance wit an image, design or character upon a body which comprises a resinous compound derived from B-nap-hthylamine and a five-membered mono-heterocyclic compound, said body having associated there--' with a sensitizing agent comprising a halogen-liberating compound.

17. A photographic process which com-.

prises: acting selectively with light in accordance with an image, design or character comprising a solution of a resinous compound derived from B-naphthylamine and a five-membered mono heterocyclic compound and film in' accordance character.

20. A photographic pi'hcess which comwith an image, design or acting selectively with light upon said prises: applying to a suitable surface a film comprising a solution of aresinous compound derived from B-naphthylamine and a five-membered mono-heterocyclic compound, associated with a sensitizer acting selectively With light upon said filmin accordance with an image, design or character;

and developing the film.

21. A photographic process which comprises: applying to a suitable surface a film comprising a solution of a compound derived by combining, an amine with a fivemembered mono-heterocyclic compound, said solution containing also a sensitizing agent comprising a halogen-liberating compound; and acting selectively with light upon said film in accordance with an image design or character.

22. A photographic process which comprises: combining B-naphthylamine with a five-membered mono-heterocyclic compound, incorporating in said compound a sensitizing agent comprising a halogen-liberating compound; acting selectively withlight upon said compound in accordance with an image, design or character, to effect selective transformation of the compound; and developing the image.

23. The process of producing a photographic medium which comprises: incor porating with a resinous compoundderived from an amine and a-five-membered monoheterocycllc compound, a sens1t1z1ng agent.

graphic medium which comprises: incorporatlng w1th a resinous compound derived from an amine and a 'five-membered monoheterocyclic compound, a sensitizing agentfrom an amine and a five-membered mono- .120 24. The process of producing. a photoy heterocyclic compound, a sensitizing agent comprising a halogen-liberating compound.

26. The process of producing a photographic medium which comprises: incor porating with a resinous compound derived from an amine and a five-membered monoheterocyclic compound, a sensitizing agent gomprising a halogen-substituted hydrocar- 27. The process of producing a photographic medium which comprises: incorporating with a resinous compound derived from an amine and a five-membered monoheterocyclic compound, a sensitizing agent comprising iodoform.

28. The process of producing a photographic medium which comprises: formin a solution of a resinous product derive by combining an amine with a five-membered mono-heterocyclic compound,'and incorporating in said solution a sensitizing agent.

. 29. The process of producing a photographic medium which comprises: forming a solution of a resinous product derived by combining an amine with a five-membered mono-heterocyclic compound, and incorporating in said solution a sensitizing agent comprising a halogen-liberating compound.

30. The process of producing a photographic medium which com rises: forming a solution of a resinous pro uct derived by combining an amine with a five-membered mono-heterocyclic compound, and incorporating in said solution a sensitizing agent gomprising a halogen-substituted hydrocar- 31. The process of producing a photographic medium which comprises: formin a solution of a resinous product derive 'by' combining an amine with a five-memresinous compound comprising a halogen source. I

. 34. A photographic medium comprising a resinous compound derived from an amine and a five-membered mono-heterocyclic compound, and a sensitizer incorporated in said resinous compound comprising a halogen liberating compound.

' 3 5. A photographic medium comprising a resinous compound derived from an amine and a five-membered mono-heterocychc compound, and a sensitlzer incorporated in said resinous compound comprising a halogensubstituted hydrocarbon.

36, A photographic medium comprising a resinous compound derived from an amine and a five-membered mono-heterocyclic compound, and a sensitizer incorporated in said rcsinouscompound comprising iodoform.

37. A photographic medium comprisinga resinous compound derived from B-naphthylamine and a five-membered mono-heterocyclic compound, and a sensitizer incorporated in said compound.

38. A photographicmedium comprising a resinous compound derived from B-naphthylamine and a five-membered mono-heterocyclic compound, and a sensitizer incorporated in said compound comprising a halogen source.

39. A photographic medium comprising a resinous compound derived from B-naphthylamine and a five-membered mono-heterocyclic compound, and a sensitizer incorporated in said compound comprising a halogen-liberating compound.

40. A photographic medium comprising a resinous compound derived from B-naphthylamine and a five-membered mono-heterocyclic compound, and a sensitizer incor 0- rated in said compound comprising io 0- form.

'41. A photographic medium comprising a resinous compound derived from B-naphthylamine and furfural, said compound having incorporated therewith a sensitizing agent.

'42. A photographic medium comprising a resinous compound derived from B-naphthylamine and furfural, said compound having incorporated therewith a sensitizing agent comprising a halogen source.

43. A photographic medium comprising a. resinous compound derived from B-naphthylamine and furfural, said compound having incorporated therewith a sensitizing agentZ11 comprising a halogen-liberating compoun 44. A photographic medium comprising'a resinous compound derived from B-naphthylamine and furfural, said compound having incorporated therewith a sensitizing agent comprising iodoform.

45. A photographic medium comprising a solution of a resinous compound derived from B-naphthylamine and furfural, said solution having incorporated therein a sensitizing agent.

46. A photographic medium comprising a solution of a resinous compound derived from B-naphthylamine and furfural, said solution having incorporated therein a sensitizin agent comprising a.halogen source.

47. photographic medium comprising a solution of a' resinous compound derived from B-naphthylamine and furfural, "said solution having incorporated therein a sensitizing agent comprising a halogen-substituted hydro-carbon.

48. A photographic medium comprising a solution of a resinous compound derived from- B-naphthylamine and furfural, said compound and embodying an image, character or design.

50. A p otographic print embodying an image, design or character which comprises a. condensation product derived from an .1

amine and a five-membe'red mono-heterocychc compound.

51. A photographicprint embodying an image, design or character comprising a condensation product of B-naphthylamine 0 and furfural'.

In testimony whereof we afiix our signatures.

MURRAY 0. BEEBE.

ALEXANDER MURRAY. HAROLD V. HERLINGER. 

